Anthraquinone vat dyestuffs



United States Patent ice Patented 3 31 1 2,706,731 such compounds consists, for example, diazotizing l-amino-2-methyl-4- or -5-chlorobenzene Wlth the ald of ANTHRAQUINONE VAT DYESTUFFS hydrofluoric acid and sodium nitrite, the appropriate fluorine substitution product being formed either simul- Eduard M f Basel i g to Clba 5 taneously with diazotization by the action of the hydro- Lumted Basel Swltze'an a rm fluoric acid or by subsequent conversion 3f the giafio D 1 1 1 compound into the fluorine substitution pro uct wit t e ?f gfigf ig gfggg'a f g ggfiz g splitting off of nitrogen. In the resultlng l-fluoro-2- methyl-4- or -5-chlorobenzene the methyl group is either 1954 senal 433307 oxidized directly to a carboxylic acid group or converted Claims priority, application Switzerland June 3, 1949 into a trichloromethyl group followed by hydrolysis of the latter to a carboxylic acid group.

The Porno of the f i gg i s to The 1-amino-5-(2-fluoro benzoylamino) anthraqui- November 197 as een Sc alme none or 122t1lmino-5-(2 fiuoro-4I 0C1; -5'i;:hlorober11zoylamino)- an raquinone are acy ate wit an acy ating 4 Chums: F 260 327) k agent derived from thianthrene dicarboxylic acid. This application is a dwlslon Of my copendmg aP191163 In all cases it is of advantage to carry out the acylation Se.na1 N 1 fi on December 2 with the air of reactive derivatives of the carboxylic WhlCh 1tself 1s a continuation in part of my applicatlon acid in question The reaction may be Conducted in a Serial No. 100,298, filed June 20, 1949, the latter being solvent or dispersing medium advantageously of high now abandoned.

The present invention is based on the observation that i pomt Such as mono d1 9 m chlorobenzene valuable vat dyestulfs are produced when one molecular mtrobenzen? naphthalene at a ralsed tempoefature, proportion of an acylating agent derived from thianthrene e f Yvlthln the relflge f1'0m ab0l1 t 0 t0 the dicarboxylic acid is reacted with two molecular proporbolllng Polnt 0f the Solvent dlspefslng medlum usedtions of 1-amino-5-(2-fluorobenzoylamino)-anthraqui The Products of the lnventlon are Valuable Vat y none, l-amino-S-(4-ch101'0-2'-flu0robenzoy1amin0)- stuifs. They can be used in known manner as such or thraquinone or l-amino-S-(5'-chloro-2-fiuorobenzoyl- 1n the form of their leuco-ester salts obtainable by known amino)-anthraquinone. methods for dyeing and printing a very wide variety of Accordingly the new dyestuffs correspond to the fibers of animal and especially vegetable character, thus formula wool and silk, but especially cotton, linen, and artificial S I 0 HN-OC C O-NH wherein R stands for a member selected from the group silk or staple fibers of regenerated cellulose and also consisting of the radicals corresponding to the formulae superpolyamide fibers.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

C1 Example 1 Y A mixture 3.04 parts of thianthrene-dicarboxylic acid (obtained as disclosed in U. S. Patent No. 2,338,516), 01 16 parts of thionyl chloride, 0.05 part of pyridine and 290 parts of trichlorobenzene is heated in about 2 hours from C. to boiling temperature. Then 60 parts of the solvent are distilled off and 7.5 parts of l-amino-S- 60 (2'-fluorbenzoylamino)-anthraquinone are added at about C. and the whole is heated again to boiling and 1-amino-5-(4- or 5'-chloro-2-fluorobenzoylamino)-ankept at this temperature for 2 hours while stirring. The thraquinone can be prepared by monoacylation of 1:5-didifiicultly soluble dyestufl of the formula Qoo-Nn o o HN-OCQ l o HN-OC co-Nn o \S/ aminanthraquinone. The 2-fiuoro-4- or -5-chlorobenis filtered off at C. and washed with alcohol. It zoic acid which are necessary for introducing the coris soluble in concentrated sulfuric acid with an orange responding acyl radicals can be made by methods in 0 coloration and dyes cotton from a bordeaux colored themselves known. A suitable method for preparing hydrosulfite vat in very fast golden yellow shades.

The l-amino-S (ortho-fluorobenzoylamino -anthraquinone employed can be obtained by partial acylation of 1zS-diamino-anthraquinone with ortho-fiuorobenzoyl chloride or from 1-chloro-5-(ortho-fiuorobenzoylamino) anthraquinone by replacement of the chlorine atom by 5 the toluene sulfonamide residue and splitting ofi of the sulfonic acid residue. It crystallizes from pyridine or nitrobenzene in fine red crystals which melt at 269.5-270 C. (uncorrected).

Example 2 A mixture of 1.12 parts of thianthrene dicarboxylic acid of the constitution such as is used in British Patent No. 555,055, 6 parts of thionyl chloride, 0.05 part of pyridine and 90 parts of trichlorobenzene is stirred for minutes at C. and for a further 30 minutes at 120 C., and is then heated at the boil, whereupon thionyl chloride and some of the solvent distil off. The solution is allowed to cool to C., 3 parts of 1-amino-5-(2'- fluoro-4'-chlorobenzoylarnino)-anthraquinone are added and the whole is heated for 2 hours at ZOO-210 C After cooling to about 120 C. the dyestulf of the formula (HQ-C o-HN o Q-o ONH 0 quinone (melting point 269 C.) can be made in the same manner.

2-fluoro-4-chlorobenzoyl chloride (boiling at 106 C. under 14 mm. pressure) can be made from Z-fluoro- 4-chlorobenzoic acid (melting point 205 C.) by reaction with thionyl chloride.

The 2-fluoro-4-chlorobenzoic acid can advantageously be prepared by the oxidation with potassium permanganate of 2-fiuoro-4-chlorotoluene (boiling at 158 C. under 743 mm. pressure, which latter can be obtained from 2-amino-4-chlorotoluene by the hydrofiuoboric acid method of Balz and Schiemann (Berichte der deutschen Chemischen Gesellschaft, vol. 60, page 1188 (1927)) in excellent yield. In an analogous manner 2-flouro- S-chlorobenzoyl chloride (boiling at l03l04 C. under 15 mm. pressure) can be obtained from 2-amino-5-chlorotoluene by way of the intermediate products 2-fluoro-5- chloro-toluene (boiling at 156 C. under 741 mm. pressure) and Z-fluoro-S-chlorobenzoic acid (melting at 149-150 C.).

What is claimed is:

1. An anthraquinone vat dyestuif of the formula NH-C O-R o H l s i I l Q I 0 HN-OC CO-NH d wherein R stands for a member selected from the group and 2. The anthraquinone vat dyestuft of the formula 3. The anthraquinone vat dyestuff of the formula 5 4. The anthraquinone vat dyestufi of the formula 01 G1 I I 6 i I 1% s I g HN-OC CO-NH 0 References Cited in the file of this patent UNITED STATES PATENTS 2,338,516 Kern et a1. Jan. 4, 1944 2,693,473 Moergeli et a1. Nov. 2, 1954 

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA 